CN101120040B - Method for compounding polycondensates - Google Patents

Method for compounding polycondensates Download PDF

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CN101120040B
CN101120040B CN2006800051115A CN200680005111A CN101120040B CN 101120040 B CN101120040 B CN 101120040B CN 2006800051115 A CN2006800051115 A CN 2006800051115A CN 200680005111 A CN200680005111 A CN 200680005111A CN 101120040 B CN101120040 B CN 101120040B
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acid
compound
polyester
ester
mixture
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CN101120040A (en
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D·舍尔策
A·艾佩尔
C·魏斯
山本基仪
G·斯库平
U·维特
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Abstract

The present invention relates to a method for compounding polycondensates selected from the group consisting of polyamide, polyester and polycarbonate in the presence of an epoxy group-containing styrene and/or (meth)acrylic monomer, a bisphenol-A-epoxy or an epoxy group-containing natural oil or fatty acid ester. The invention is characterized in that the compounding is carried out at temperatures of less than or equal to 220 DEG C and in the presence of an activator selected from the group consisting of: zinc-, titanium compound and C1-C12 alkyltriphenylphosphonium halogenide.

Description

The method of compounding polycondensates
The present invention relates to a kind of vinylbenzene that contains epoxy group(ing) and/or (methyl) acrylic monomer contain the natural oil of epoxy group(ing) or fatty acid ester in the presence of compounding be selected from the homopolymerization of polymeric amide, polyester and polycarbonate or improving one's methods of copolymerization-polycondensation thing.
The method of compounding PET is for example known by US2004/0147678 in the presence of the vinylbenzene that contains epoxy group(ing) and/or (methyl) acrylic monomer.The typical process temperature of PET is 240-300 ℃.
Yet, the compounding at a lower temperature of many polymkeric substance.Especially biological polymer such as polyhydroxyalkanoatefrom are decomposing under 200 ℃ temperature.Other biological polymer obviously decomposes being higher than under 200 ℃ the temperature.Fusion volumetric flow rate (MVR) raises.For blowing, no longer can process the high viscosity melt for some application.
Purpose of the present invention is to find a kind of method that does not have by the shortcoming of US2004/0147678 currently known methods.
Surprisingly this purpose is passed through zn cpds, titanium compound or C 1-C 12Alkyl triphenyl phosphonium halide adds melt and realizes.The expanding material that contains epoxy group(ing) activates by above-claimed cpd and even can resist chain degradation being lower than under 220 ℃ the temperature.
This method is fit to the polycondensate that compounding is selected from polymeric amide, polyester and polycarbonate in principle.
The inventive method is fit to especially that preparation is selected from polylactide, polycaprolactone, polyhydroxyalkanoatefrom and the biodegradable equal polyester or the copolyesters of the polyester be made up of aliphatic series and/or aromatic dicarboxylate and aliphatic diol.
All polyester based on aliphatic series and aromatic dicarboxylate and aliphatic dihydroxy compound that are known as the partially aromatic polyester also are useful.The mixture that is understood that multiple this kind polyester also is suitable as polycondensate.
According to the present invention, the partially aromatic polyester will also be understood that and is polyester derivatives such as polyether ester, polyesteramide or polyether ester amides.Suitable partially aromatic polyester comprises linearity, does not increase the polyester (WO92/09654) of chain.Preferably increase the partially aromatic polyester of chain and/or branching.The latter is by the document WO 96/15173-15176 that introduces fully as a reference, 21689-21692,25446,25448 and WO98/12242 known.The mixture of distinct portions aromatic polyester is useful equally.The partially aromatic polyester especially comprise such as
Figure S06805111520070820D000021
(BASF Aktiengesellschaft) and
Figure S06805111520070820D000022
The product of Bio (Novamont).
Especially preferred partially aromatic polyester comprises and wherein comprises the polyester of following material as main ingredient:
A) acid constituents of forming by following material:
A1) derivative or its mixture of at least a aliphatic dicarboxylic acid of 30-99 mole % or at least a alicyclic di-carboxylic acid or its formation ester,
A2) at least a aromatic dicarboxylate of 1-70 mole % or its form the derivative of ester or its mixture and
A3) compound that contains sulfonate radical of 0-5 mole %,
B) be selected from least a C 2-C 12Alkanediol and at least a C 5-C 10The diol component of cycloalkanes glycol or its mixture,
And extra if necessary one or more are selected from following component:
C) be selected from following component:
C1) comprise at least one ether functional group and have the dihydroxy compound of formula I:
Figure S06805111520070820D000023
Wherein n be 2,3 or 4 and m be the integer of 2-250,
C2) hydroxycarboxylic acid of at least a formula IIa or IIb:
Figure S06805111520070820D000024
Wherein p is the integer of 1-1500, and r is the integer of 1-4, G for be selected from phenylene ,-(CH 2) q-,-C (R) H-and-C (R) HCH 2Group, wherein q is the integer of 1-5, R is methyl or ethyl,
C3) at least a amino-C 2-C 12Alkanol or at least a amino-C 5-C 10Cycloalkanol or its mixture,
C4) at least a diamino-C 1-C 8Paraffinic hydrocarbons,
C5) 2 of at least a general formula III, 2 '-bisoxazolines:
R wherein 1Be singly-bound, wherein z=2,3 or 4 (CH 2) z-alkylidene group or phenylene,
C6) at least a be selected from natural amino acid, can be by di-carboxylic acid and have an aminocarboxylic acid of polymeric amide, formula IVa and IVb compound that the diamines polycondensation of 4-10 carbon atom obtains with 4-6 carbon atom:
Figure S06805111520070820D000031
Wherein s is the integer of 1-1500, and t is the integer of 1-4, and T is selected from following group: phenylene, wherein u be the integer of 1-12-(CH 2) u-, R wherein 2For methyl or ethyl-C (R 2) H-and-C (R 2) HCH 2,
And have repeating unit V De Ju oxazoline:
R wherein 3Be hydrogen, C 1-C 6Alkyl, C 5-C 8Cycloalkyl, do not replace or by C 1-C 4Alkyl is trisubstd phenyl at the most, or tetrahydrofuran base,
Or the mixture of c1-c6,
With
D) be selected from following component:
D1) at least a have at least three compounds that can form the group of ester,
D2) at least a isocyanic ester,
D3) at least a divinyl ether,
Or d1)-d3) mixture.
In preferred embodiments, the acid constituents A of partially aromatic polyester comprises 30-70 mole %, especially 40-60 mole %a1, and 30-70 mole %, especially 40-60 mole %a2.
Useful aliphatic acid and corresponding derivative a1 are generally has 2-10 carbon atom, those of preferred 4-6 carbon atom.They can be linearity or branching.Can be used for alicyclic di-carboxylic acid in the context of the invention and be generally and have 7-10 carbon atom, especially have those of 8 carbon atoms.Yet, also can use in principle to have the greater number carbon atom as having the di-carboxylic acid of 30 carbon atoms at the most.
Example comprises: toxilic acid, succsinic acid, pentanedioic acid, 2-methylglutaric acid, 3-methylglutaric acid, hexanodioic acid, pimelic acid, nonane diacid, sebacic acid, fumaric acid, 2,2-dimethylated pentanedioic acid, suberic acid, 1,3-pentamethylene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, diglycollic acid, methylene-succinic acid, toxilic acid and 2,5-norbornane dicarboxylic acid.
The derivative of the formation ester of same above-mentioned aliphatic series of available or alicyclic di-carboxylic acid especially is two C 1-C 6Alkyl ester such as dimethyl esters, diethyl ester, di ester, diisopropyl ester, di-n-butyl ester, diisobutyl ester, di-t-butyl ester, two n-pentyl esters, diisoamyl ester or di-n-hexyl ester.Can use the acid anhydrides of di-carboxylic acid equally.
The derivative that di-carboxylic acid or its form ester can use separately or two or more mixture uses with it.
Especially preferably use derivative or its mixture of hexanodioic acid, sebacic acid or its specific formation ester.Especially preferably use hexanodioic acid or its to form derivative such as its alkyl ester or its mixture of ester.
Suitable aromatic dicarboxylate a2 is generally has 8-12 carbon atom, preferably has those of 8 carbon atoms.Example comprises terephthalic acid, m-phthalic acid, 2,6-naphthoic acid and 1, the 5-naphthoic acid with and form the derivative of ester.Especially should mention two C 1-C 6Alkyl ester, for example dimethyl esters, diethyl ester, di ester, diisopropyl ester, di-n-butyl ester, diisobutyl ester, di-t-butyl ester, two n-pentyl esters, diisoamyl ester or di-n-hexyl ester.The acid anhydrides of di-carboxylic acid a2 is the same suitable with the derivative that forms ester.
Yet, also can use in principle to have the greater number carbon atom as the aromatic dicarboxylate a2 of 20 carbon atoms at the most.
The derivative a2 that aromatic dicarboxylate or its form ester can use separately or two or more mixture uses with it.Especially preferably use terephthalic acid or its to form the derivative such as the dimethyl terephthalate (DMT) of ester.
The used compound that contains sulfonate radical is generally the di-carboxylic acid that contains sulfonate radical or it forms the basic metal or the alkaline earth salt of the derivative of ester, an alkali metal salt or its mixture, the more preferably sodium salt of preferred 5-sulfoisophthalic acid.
In a preferred embodiment, acid constituents A comprises 40-60 mole %a1,40-60 mole %a2 and 0-2 mole %a3.In another preferred embodiment, acid constituents A comprises 40-59.9 mole %a1,40-59.9 mole %a2 and 0.1-1 mole %a3, especially 40-59.8 mole %a1,40-59.8 mole %a2 and 0.2-0.5 mole %a3.
Usually, glycol B is selected from has 2-12 carbon atom, the preferably branching or the linear alkanediol of 4-6 carbon atom, or have the cycloalkanes glycol of 5-10 carbon atom.
The example of suitable alkanediol is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 2,2,4-trimethylammonium-1,6-hexylene glycol, especially ethylene glycol, 1, ammediol, 1,4-butyleneglycol and 2 (neopentyl glycol); Ring pentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol or 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Also can use the mixture of different alkanediols.
Whether depend on needs excessive acid or OH end group, can use excessive component A or B component.In preferred embodiments, the mol ratio of used component A and B is 0.4:1-1.5:1, preferred 0.6:1-1.1:1.
Except component A and B, polyester mixture of the present invention based on polyester can comprise other component.
Used dihydroxy compound c1 is preferably glycol ether, triglycol, polyoxyethylene glycol, polypropylene glycol and polytetrahydrofuran (poly-THF), more preferably glycol ether, triglycol and polyoxyethylene glycol, and also can use its mixture, or for example can be by at first making oxyethane, make the compound with different variable n (referring to formula I) that propylene oxide obtains by known method polymerization itself as comprising the polyoxyethylene glycol of propylidene unit (n=3) then, more preferably based on the polymkeric substance of the polyoxyethylene glycol with different variable n, unit is wherein mainly formed by oxyethane.Usually at 250-8000g/mol, select the molecular weight (M of polyoxyethylene glycol in the scope of preferred 600-3000g/mol n).
In a preferred embodiment, can will be 15-98 mole % for example based on B and c1 molar weight, preferred 60-99.5 mole % glycol B, and 0.2-85 mole %, preferred 0.5-30 mole % dihydroxy compound c1 is used to prepare the partially aromatic polyester.
In preferred embodiments, used hydroxycarboxylic acid c2) be: oxyacetic acid, D-, L-or D, L-lactic acid, 6 hydroxycaproic acid, its cyclic derivatives such as glycollide (1,4-diox-2, the 5-diketone), and the two rac-Lactides of D-or L-(3,6-dimethyl-1,4-diox-2, the 5-diketone), P-hydroxybenzoic acid, or its oligopolymer and poly-3-hydroxy alkane acid ester such as polyhydroxybutyrate, poly-hydroxypentanoic acid, polylactide are (for example passable
Figure S06805111520070820D000051
2000D (Cargill) obtains), or the mixture of poly-3-hydroxybutyric acid and poly-hydroxypentanoic acid (wherein the latter is passable
Figure S06805111520070820D000061
Obtain from Zeneca), or poly-3-hydroxybutyric acid and poly (hydroxy alkanoate) are as other multipolymer of poly-hydroxycaproic acid or poly-Hydroxyoctanoic acid; Be preparation partially aromatic polyester, preferred especially its lower molecular weight and cyclic derivative.
The consumption of hydroxycarboxylic acid for example can be 0.01-50 weight % based on the amount of A and B, preferred 0.1-40 weight %.
Used amino-C 2-C 12Alkanol or be intended to comprise the amino-C of 4-amino methyl cyclohexane methanol 5-C 10Cycloalkanol (amount of component b 3) is preferably amino-C 2-C 6Alkanol such as 2-monoethanolamine, amino amylalcohol of 3-aminopropanol, 4-amino butanol, 5-or 6-amino-hexanol, or amino-C 5-C 6The pure and mild Trans-4-Amino Cyclohexanol of cycloalkanol such as amino cyclopentyl, or its mixture.
Used diamino-C 1-C 8Paraffinic hydrocarbons (amount of component b 4) is preferably diamino-C 4-C 6Paraffinic hydrocarbons is as 1,4-diaminobutane, 1,5-diamino pentane or 1 (hexamethylene-diamine, " HMD ").
In the preferred embodiment of preparation partially aromatic polyester, can use molar weight to be 0.5-99.5 mole % based on B, preferred 0.5-50 mole %c3, and be 0-50 mole % based on the molar weight of B, preferred 0-35 mole %c4.
2 of general formula III, 2 '-bisoxazoline c5 usually can be via Angew Chem.Int.Edit., the 11st volume (1972), the method for 287-288 page or leaf obtains.Particularly preferred bisoxazoline is R wherein 1Be singly-bound, wherein z=2,3 or 4 (CH 2) z-alkylidene group such as methylene radical, ethane-1,2-two bases, propane-1,3-two bases or propane-1, those of 2-two bases or phenylene.Particularly preferred bisoxazoline comprises 2,2 '-two (2-oxazolines), two (2-oxazolinyl) methane, 1, two (2-oxazolinyl) ethane, 1 of 2-, two (2-oxazolinyl) propane and 1 of 3-, two (2-oxazolinyl) butane of 4-, especially 1, two (2-oxazolinyl) benzene, 1 of 4-, two (2-oxazolinyl) benzene or 1 of 2-, two (2-oxazolinyl) benzene of 3-.
For preparation partially aromatic polyester, based on the integral molar quantity of B component, c3, c4 and c5, for example can use 70-98 mole %B in each case, at the most 30 moles of %c3 and 0.5-30 mole %c4 and 0.5-30 mole %c5.In another preferred embodiment, can use 0.1-5 weight % based on the gross weight of A and B, the c5 of preferred 0.2-4 weight %.
Used amount of component b 6 can be the aminocarboxylic acid of natural generation.These comprise Xie Ansuan, leucine, Isoleucine, Threonine, methionine(Met), phenylalanine, tryptophane, Methionin, L-Ala, arginine, aspartic acid, halfcystine, L-glutamic acid, glycine, Histidine, proline(Pro), Serine, tyrosine, l-asparagine and glutamine.
The aminocarboxylic acid of preferred general formula I Va and IVb is the integer of 1-1000 for s wherein, and t is 1-4, preferred 1 or 2 integer, and T be selected from phenylene and wherein u be 1,5 or 12-(CH 2) those of u-.
C6 also can be general formula V De Ju oxazoline.Yet c6 also can be the mixture of different aminocarboxylic acids and/or Ju oxazoline.
In preferred embodiments, the consumption of c6 is 0.01-50 weight % based on the total amount of component A and B, preferred 0.1-40 weight %.
Can choose other component that is used to prepare the partially aromatic polyester wantonly comprises and comprises at least three compound d 1 that can form the group of ester.
Compound d 1 preferably comprises 3-10 the functional group that can form ester bond.Particularly preferred compound d 1 has 3-6 this class functional group, especially 3-6 hydroxyl and/or carboxyl in molecule.Example comprises:
Tartrate, citric acid, toxilic acid;
TriMethylolPropane(TMP), trimethylolethane;
Tetramethylolmethane;
Polyether triol;
Glycerine;
1,3, the 5-benzenetricarboxylic acid;
Trimellitic acid, trimellitic acid 1,2-anhydride;
Pyromellitic acid, pyromellitic dianhydride and
The hydroxyl m-phthalic acid.
The consumption of compound d 1 is 0.01-15 mole % based on component A usually, preferred 0.05-10 mole %, more preferably 0.1-4 mole %.
Used component d2 is the mixture of a kind of isocyanic ester or different isocyanic ester.Can use aromatics or aliphatic vulcabond.Yet, also can use the isocyanic ester of higher functionality.
In the context of the invention, aromatic diisocyanate d2 especially is a toluene 2,4-vulcabond, toluene 2,6-vulcabond, ditan 2,2 '-vulcabond, ditan 2,4 '-vulcabond, ditan 4,4 '-vulcabond, naphthylidene 1,5-vulcabond or xylylene diisocyanate.
Wherein, preferred especially ditan 2,2 '-vulcabond, ditan 2,4 '-vulcabond and ditan 4,4 '-vulcabond is as component d2.Back one vulcabond uses with mixture usually.
Also spendable three ring isocyanic ester d2 are three (4-isocyano-phenyl) methane.The polycyclic aromatic vulcabond for example obtains in the process of preparation one ring or two ring vulcabond.
Component d2 also can comprise on a small quantity, for example based on the gross weight of component d2 at the most the uretdione base of 5 weight % be used for the blocked isocyanate base.
In the context of the invention, aliphatic vulcabond d2 is especially for having 2-20 carbon atom, linearity or the sub-branched alkyl vulcabond or the cycloalkylidene vulcabond of preferred 3-12 carbon atom, for example hexa-methylene 1,6-vulcabond, isophorone diisocyanate or methylene-bis (4-isocyanato-hexanaphthene).Particularly preferred aliphatic vulcabond d2 is a hexa-methylene 1,6-vulcabond and isophorone diisocyanate.
Preferred isocyanuric acid ester comprises coming to have 2-20 carbon atom, the alkylidene group vulcabond of preferred 3-12 carbon atom or the aliphatic isocyanuric acid ester of cycloalkylidene vulcabond such as isophorone diisocyanate or methylene-bis (4-isocyanato-hexanaphthene).The alkylidene group vulcabond can be linearity or branching.Be preferably based on the isocyanuric acid ester of positive hexamethylene diisocyanate especially, for example cyclic trimer, pentamer or the higher oligopolymer of positive hexamethylene diisocyanate.
Usually, the consumption of component d2 is 0.01-5 mole % based on the integral molar quantity of A and B, preferred 0.05-4 mole %, more preferably 0.1-4 mole %.
Used divinyl ether d3 can be any routine and commercially available divinyl ether usually.Preferred use 1,4-butyleneglycol divinyl ether, 1,6-hexylene glycol divinyl ether or 1,4 cyclohexane dimethanol divinyl ether or its mixture.
The consumption of divinyl ether is preferably 0.01-5 weight %, especially 0.2-4 weight % based on the gross weight of A and B.
The example of preferred partially aromatic polyester is based on following component:
A、B、d1
A、B、d2
A、B、d1、d2
A、B、d3
A、B、c1
A、B、c1、d3
A、B、c3、c4
A、B、c3、c4、c5
A、B、d1、c3、c5
A、B、c3、d3
A、B、c3、d1
A、B、c1、c3、d3
A、B、c2
Wherein, be preferably based on A, B and d1 especially, or A, B and d2, or the partially aromatic polyester of A, B, d1 and d2.In another preferred embodiment, the partially aromatic polyester is based on A, B, c3, c4 and c5 or A, B, d1, c3 and c5.
Mentioned partially aromatic polyester and polyester mixture of the present invention are biodegradable usually.
In the context of the invention, when having at least 60% biological degradability when material or substance mixture define in three methods at least one in DIN V54900-2 (pre-standard in September, 1998) in, then this material or substance mixture have the feature of " biological degradability ".
Usually, biological degradability causes polyester or polyester mixture to rupture in the suitable and verifiable time.Degraded can enzyme catalysis, hydrolysis, oxidation and/or undertaken by electromagnetic radiation such as the effect of UV radiating, and is mainly caused by the effect of microorganism such as bacterium, yeast, fungi and algae usually.Biological degradability for example can quantize by polyester and compost being mixed and storing certain hour.For example, make not contain CO according to the method 3 of DIN EN13432 or DIN V54900-2 2Air compost by slaking and make compost stand defined temperature distribution in composting process.In this case, biological degradability is via the CO that discharges in the sample 2Clean amount (deduct the CO that compost under the no sample situation discharges 2After the amount) CO that discharges with sample 2Maximum possible (calculating) by carbon content in the sample ratio and measure, wherein this ratio is defined as biological degradability percentage ratio.Even at compost after a couple of days, biodegradable polyester or biodegradable polyester mixture show significant signs of degradation such as mould-growth, cracking and perforation usually.
Other method of measuring biological degradability for example is described among ASTM D5338 and the ASTM D6400.
The preparation of partially aromatic polyester itself is known maybe can be undertaken by known method itself.
Preferred partially aromatic polyester be characterized as its molecular weight (M n) be 1000-100000g/mol, especially 9000-75000g/mol, preferably 10000-50000g/mol, and its fusing point is 60-170 ℃, preferred 80-150 ℃.
Described partially aromatic polyester can have the hydroxyl and/or the carboxyl end groups of any required ratio.But mentioned partially aromatic polyester is terminal groups modification also.For example the OH end group can be by the sour modification with the reaction of phthalic acid, Tetra hydro Phthalic anhydride, trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid or PMA.
Suitable polycondensate also is preferably the equal polyester of the polyester that is selected from polylactide, polycaprolactone, polyhydroxyalkanoatefrom and aliphatic dicarboxylic acid and aliphatic diol or the biodegradable polyester mixture of copolyesters.
Preferred polycondensate also is polylactide (PLA) and polyhydroxyalkanoatefrom, at this especially poly butyric ester (PHB) and polyhydroxybutyrate valeric acid copolyesters (PHBV).Especially the product that comprises for example is
Figure S06805111520070820D000101
(available from the polylactide of Cargill Dow),
Figure S06805111520070820D000102
(available from the poly butyric ester of PHB Ind.);
Figure S06805111520070820D000103
(available from the polyhydroxybutyrate valeric acid copolyesters of Tianan).
Preferred expanding material is for example for containing vinylbenzene and/or (methyl) acrylic monomer of epoxy group(ing).This compound has two or more epoxy group(ing) usually in molecule.Especially suitable is oligomeric or polymeric epoxidation compound as by Johnson Polymers with the trade mark
Figure S06805111520070820D000104
ADR4367 or Two-or two-or the poly glycidyl ester of polycarboxylic acid more that ADR4368 sells, or two-or two-or polyglycidyl ether of polyvalent alcohol more, or the multipolymer of vinylbenzene and (methyl) glycidyl acrylate, or by Resolution Performance Products for example with The glycidyl ether of 828 dihydroxyphenyl propanes of selling.
Other preferred expanding material is the compound that comprises at least one carbon-to-carbon double bond or three key and at least one epoxy group(ing) in the molecule.Glycidyl acrylate and glycidyl methacrylate are especially suitable.
Also preferably by containing the expanding material that epoxy group(ing) (epoxidised) natural oil or fatty acid ester are formed.Natural oil for example is interpreted as the mixture of sweet oil, Toenol 1140, soya-bean oil, plam oil, peanut oil, Oleum Cocois, algal oil, fish oil or these compounds.Especially preferred epoxidised soya-bean oil (for example available from Hobum, Hamburg's
Figure S06805111520070820D000107
ESBO, or available from Cognis, Dusseldorf's
Figure S06805111520070820D000108
B316) or epoxidised Toenol 1140 (for example available from Hobum, Hamburg's ELO).
Preferred the inventive method is fit to preparation example as comprising as component i
Figure S06805111520070820D000112
For example as component ii's
Figure S06805111520070820D000113
Or
Figure S06805111520070820D000114
The biodegradable polyester mixture.These mixtures comprise 5-90 weight % usually, preferred 10-70 weight %, more preferably 15-60 weight %, especially the component i of 20-50 weight %, and 10-95 weight %, preferred 30-90 weight %, more preferably 40-85 weight %, the component ii of 50-80 weight % most preferably, wherein each weight percent number average is based on the gross weight of component i-ii and itself be 100 weight %.
For the production of film, bubble stability has very big importance.Found now that wherein component i forms external phase and component ii has good bubble stability with the mixture that separation region embeds this phase.Mixture has the 45 weight % of surpassing based on the gross weight of component i and ii (polycondensate) in each case, preferably surpasses the component i of 50 weight %, thereby makes component i form external phase.
The inventive method is usually at 0.1-5 weight % in addition, and preferred 0.1-2 weight % more preferably carries out under the existence of 0.3-1 weight % expanding material, and wherein each weight percent number average is based on the gross weight of polycondensate.
For the purpose of the present invention, activator is zn cpds, titanium compound or C 1-C 12Alkyl triphenyl phosphonium halide.Useful activator especially is a Zinic stearas, titanic hydroxide four C 1-C 6Alkyl ester such as titanic hydroxide tetrabutyl ester, or ethyl triphenyl phosphonium bromide.
Activator to be being 0.1-10 weight % based on polycondensate, preferred 0.1-5 weight %, and more preferably the concentration of 0.1-1 weight % is used.
Known but non-other component required in this invention of those skilled in the art can be added in the melt compounded thing of the present invention, described other component for example is conventional additives such as stablizer, neutralizing agent, lubricant and releasing agent, release agent, dyestuff or the filler in the plastics technology.Useful stablizer for example comprises antioxidant such as sterically hindered phenol.This can resist other oxidative degradation of polycondensate.
Biologically-degradable polyester mixture of the present invention can pass through currently known methods (EP792309 and US5,883,199) by each component preparation.
For example can be under the temperature that raises such as 120-220 ℃, in the known mixing equipment of those skilled in the art such as kneader or forcing machine, all components i, ii and expanding material are mixed in a processing step and react.
By the inventive method, processing produces the anti-biodegradable polymeric blends that pierces through film to have obtained (having stable bubble) without difficulty.
Embodiment:
Performance test:
The molecular weight M of following mensuration part aromatic polyester n:
15mg partially aromatic polyester is dissolved in the 10mi hexafluoroisopropyl alcohol (HFIP).Analyze 125 these solution of μ l by gel permeation chromatography (GPC) in each case.At room temperature measure.HFIP+0.05 weight % trifluoroacetic acid potassium is used for wash-out.Elution rate is 0.5ml/min.Use following column combination (all posts are made by the Showa Denko Ltd. of Japan):
Figure S06805111520070820D000121
HFIP-800P (diameter 8mm, length 5cm),
Figure S06805111520070820D000122
HFIP-803 (diameter 8mm, length 30cm),
Figure S06805111520070820D000123
HFIP-803 (diameter 8mm, length 30cm).By RI detector (differential refractometry) test section aromatic polyester.Use molecular weight M n=505 to M nThe polymethylmethacrylate standard test specimen of=2740000 close limit is proofreaied and correct.Outside described interval, the wash-out scope is measured by extrapotation.
The fusing point of partially aromatic polyester is used available from the Exstet DSC6200R unit of Seiko and is measured by the dsc measurement method:
Under nitrogen atmosphere, the concrete sample of 10-15mg is heated to 200 ℃ by-70 ℃ with the heating rate of 20 ℃/min.The sample fusing point of being reported is observed peak temperature to melting peak.Used in each case reference substance is empty sample crucible.
The mixture of component i, ii and expanding material and prepared to be used for correlated uniformity of mixture be that the film of 30 μ m is measured by in each case these mixtures being depressed to thickness at 190 ℃.The mark of dispersed component ii not in these films of visual evaluation.
Raw material:
Component i:
I-1: be preparation polyester i-1, with 87.3kg dimethyl terephthalate (DMT), 80.3kg hexanodioic acid, 117kg1,4-butyleneglycol and 0.2kg glycerine mix with 0.028kg titanic hydroxide tetrabutyl ester (TBOT), and the mol ratio of alkoxide component and acid constituents is 1.30.With reaction mixture be heated to temperature be 180 ℃ and under this temperature the reaction 6 hours.Subsequently, elevate the temperature to 240 ℃ and under reduced pressure excessive dihydroxy compound is steamed through 3 hours.Subsequently, in 1 hour, slowly be metered into the 0.9kg hexamethylene diisocyanate at 240 ℃.
The polyester i-1 that so obtains has 119 ℃ fusing point and the molecular weight of 23000g/mol (Mn).Component ii:
ii-1：PHB/V (3％)
Figure S06805111520070820D000131
Expanding material:
Available from Johnson Polymer's
Figure S06805111520070820D000132
ADR4368.
ESBO: epoxidised soya-bean oil (for example available from Hobum, Hamburg's
Figure S06805111520070820D000133
ESBO, or available from Cognis, Dusseldorf's
Figure S06805111520070820D000134
B316).Embodiment 1-4):
Study 60 weight %
Figure S06805111520070820D000135
With 40 weight %PHB/V (3%)
Figure S06805111520070820D000136
Blend (mixture):
Experimental arrangement:
Polymkeric substance (Ecoflex-Enmat blend) is weighed in the Glass Containers on the analytical balance.Subsequently, add expanding material (and in stable experiment extra stablizer) therein, add activator subsequently.In Comparative Examples, at no activator or only have and carry out compounding under the stablizer situation.
Only before next-door neighbour's charging program, be added dropwise to the catalyzer that exists with liquid form.Pack into mixture in the funnel of right cylinder charging annex and be introduced into forcing machine by the mould in the right cylinder.Melt was circulated in the loop 3 minutes, then it is discharged by forcing machine.
Temperature: 170-171 ℃, speed of rotation: 80rpm, the residence time: 3 minutes, weight: 17g (mixture of polymkeric substance/expanding material, polymkeric substance/expanding material/activator, polymkeric substance/stablizer, polymkeric substance/expanding material/activator/stablizer)
MVR measures: 170 ℃/2.16kg
Figure S06805111520070820D000137
Figure S06805111520070820D000141
Compare with the Comparative Examples 1 that comprises expanding material but do not contain activator, the embodiment 2-7 that also comprises activator except that expanding material has shown obviously lower flow rate (MVR).

Claims (11)

  1. One kind in the presence of polymeric epoxidation compound compounding be selected from the method for the polycondensate of polymeric amide, polyester and polycarbonate, its be included in less than/equal under 220 ℃ the temperature and be that 0.3-5 weight % carries out compounding in the presence of as the Zinic stearas of activator based on polycondensate.
  2. 2. according to the process of claim 1 wherein that described polymeric epoxidation compound is oligomeric epoxidation compound.
  3. 3. according to the process of claim 1 wherein that described polycondensate is selected from polylactide, polycaprolactone, polyhydroxyalkanoatefrom for one or more and the biodegradable equal polyester or the copolyesters of the polyester be made up of aliphatic series and/or aromatic dicarboxylate and aliphatic diol.
  4. 4. according to the method for claim 2, wherein said polycondensate is selected from polylactide, polycaprolactone, polyhydroxyalkanoatefrom for one or more and the biodegradable equal polyester or the copolyesters of the polyester be made up of aliphatic series and/or aromatic dicarboxylate and aliphatic diol.
  5. 5. according to each method among the claim 1-4, wherein said polycondensate is one or more biodegradable equal polyester or copolyesters that is selected from polylactide, poly-beta-hydroxy-butanoic acid ester, beta-hydroxy-butanoic acid ester-alkanoates multipolymer and polyester, and wherein said polyester has following composition:
    A) acid constituents of forming by following material:
    A1) derivative or its mixture of at least a aliphatic dicarboxylic acid of 30-99 mole % or at least a alicyclic di-carboxylic acid or its formation ester,
    A2) at least a aromatic dicarboxylate of 1-70 mole % or its form the derivative of ester or its mixture and
    A3) compound that contains sulfonate radical of 0-5 mole %,
    Component a1 wherein)-a3) molecular fraction sum be 100% and
    B) by at least a C 2-C 12Alkanediol or C 5-C 10The diol component that cycloalkanes glycol or its mixture are formed,
    And extra if necessary one or more are selected from following component:
    C) be selected from following component:
    C1) comprise at least one ether functional group and have the dihydroxy compound of formula I:
    HO-[(CH 2) n-O] m-H (I)
    Wherein n be 2,3 or 4 and m be the integer of 2-250,
    C2) compound of at least a formula IIa or IIb:
    Figure FSB00000466220200021
    Wherein p is the integer of 1-1500, and r is the integer of 1-4, G for be selected from phenylene ,-(CH 2) q-,-C (R) H-and-C (R) HCH 2Group, wherein q is the integer of 1-5, R is methyl or ethyl,
    C3) at least a amino-C 2-C 12Alkanol or at least a amino-C 5-C 10Cycloalkanol or its mixture,
    C4) at least a diamino-C 1-C 8Paraffinic hydrocarbons,
    C5) 2 of at least a general formula III, 2 '-two
    Figure FSB00000466220200022
    The azoles quinoline:
    Figure FSB00000466220200023
    R wherein 1Be singly-bound, wherein z=2,3 or 4 (CH 2) z-alkylidene group or phenylene,
    C6) at least a be selected from natural amino acid, can be by di-carboxylic acid and have a compound of polymeric amide, formula IVa and IVb compound that the diamines polycondensation of 4-10 carbon atom obtains with 4-6 carbon atom:
    Wherein s is the integer of 1-1500, and t is the integer of 1-4, and T is selected from following group:
    Phenylene, wherein u be the integer of 1-12-(CH 2) u-, R wherein 2For methyl or ethyl-C (R 2) H-and-C (R 2) HCH 2,
    And have the poly-of repeating unit V
    Figure FSB00000466220200025
    The azoles quinoline:
    Figure FSB00000466220200026
    R wherein 3Be hydrogen, C 1-C 6Alkyl, C 5-C 8Cycloalkyl does not replace or by C 1-C 4Alkyl is trisubstd phenyl at the most, or tetrahydrofuran base,
    Or the mixture of c1-c6 and
    D) be selected from following component:
    D1) at least a have at least three compounds that can form the group of ester,
    D2) at least a isocyanic ester,
    D3) at least a divinyl ether,
    Or d1)-d3) mixture.
  6. 6. according to each method among the claim 1-4, polymerized therein epoxidation compound is the multipolymer of being made up of vinylbenzene and (methyl) glycidyl acrylate.
  7. 7. according to the method for claim 5, polymerized therein epoxidation compound is the multipolymer of being made up of vinylbenzene and (methyl) glycidyl acrylate.
  8. 8. according to each method among the claim 1-4, polymerized therein epoxidation compound is being that the concentration of 0.1-2 weight % is used based on described polycondensate.
  9. 9. according to the method for claim 5, polymerized therein epoxidation compound is based on described polycondensate to be the concentration use of 0.1-2 weight %.
  10. 10. according to the method for claim 6, polymerized therein epoxidation compound is based on described polycondensate to be the concentration use of 0.1-2 weight %.
  11. 11. according to the method for claim 7, polymerized therein epoxidation compound is based on described polycondensate to be the concentration use of 0.1-2 weight %.
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